Detergent composition

ABSTRACT

A NEW DETERGENT COMPOSITION COMPRISING IN COMBINATION, A WATER-INSOLUBLE META SALT OF AMPHOTERIC SURFACE ACTIVE AGENT AND A SUBSTANCE CAPABLE OF DISPERSING AND SOLUBILIZING THIS METAL SALT IN WATER. THIS COMPOSITION MAY BE USED EITHER INDEPENDENTLY OR BY BEING INCLUDED IN ANY KNOWN DETERGENT. IN THIS LATTER INSTANCE, THE DETERGENCY, BUBBLE-FORMING ABILITY AND DURATION OF BUBBLES OF THE BASE DETERGENT ARE GREATELY IMPROVED. IN PARTICULAR, LAUNDRY WHICH IS CLEANSED WITH THIS CONPOSITION EITHER DIRECTLY OR JOINTLY WITH A KNOWN DETERGENT IN INVARIABLY BESTOWED WITH AN ANTISTATIC PROPERTY, A RESISTIVITY TO RESOILING AND A SOIL-RELEASABILITY.

United States Patent 3,71,613 DETERGENT COMPOSITION Hideo Marumo, 5-4 Nishikubo 3-chome, Musashimo-shi, Tokyo 180, Japan No Drawing. Filed Aug. 2, 1971, Ser. No. 168,413 Claims priority, application Japan, Aug. 4, 1970, 45/68,145; May 10, 1971, 46/330,390, 46/30,391 Int. Cl. Clld 3/28, 3/30 US. Cl. 252--542 7 Claims ABSTRACT OF THE DISCLOSURE A new detergent composition comprising, in combination, a Water-insoluble metal salt of amphoteric surface active agent and a substance capable of dispersing and solubilizing this metal salt in water. This composition may be used either independently or by being included in any known detergent. In this latter instance, the detergency, bubble-forming ability and duration of bubbles of the base detergent are greatly improved. In particular, laundry which is cleansed with this composition either directly or jointly with a known detergent is invariably bestowed with an antistatic property, a resistivity to resoiling and a soil-releasability.

BACKGROUND OF THE INVENTION (a) Field of the invention The present invention is concerned with a detergent, and more particularly, it relates to a new detergent composition having an improved amphoteric surface active agent as its active component.

(b) Description of the prior art In general, it has been the practice to wash natural fibers and man-made fibers with either an anionic surface active agent such as a sodium salt of alkylbenzene sulfonate or a non-ionic surface active agent such as nonyl phenol ethylene oxide adduct. However, in case these known detergents were used, the fibers cleansed with such a detergent invariably presented a deteriorated hand feel and/or a loss of antistatic property. Therefore, it has been the usual practice to give the washed fibers an additional treatment with a soft-finishing agent and/or an antistatic agent. However, these properties which were thus added to the fibers disappeared when the fibers were washed again. On the other hand, in case the fibers were washed with known detergent mixed with a soft-finishing agent and an antistatic agent, the individual effects of these mixed detergents were not exhibited clearly but rather they served, in many cases, only to lowering of the activity of the detergent per se, Therefore, in case it was intended to use a soft-finishing agent and/or an antistatic agent, it was necessary to add these agents in a rinsing solution after cleansing or to subject the washed fibers to a separate treatment with these agents, and thus a great inconvenience was experienced.

The inventor had already accomplished a method of imparting an antistatic property to plastics by the inclusion-in a plastic by kneading-of a substance having the general formula:

N-C Hz My R-C NC Hz HO I (CHzCH2O)1H CHzC 00 x (I) wherein 3,719,613 Patented Mar. 6, 1973 R represents a hydrocarbon group having 6-22 carbon atoms,

M represents a metal,

1 represents an integer, and

x, y each represents an integer determined by the valency of the said metal.

SUMMARY OF THE INVENTION The author made an extensive research in order to find means of effecting the deposition or the adsorption of the said substance having the chemical Formula I onto the surface of a polymer-which is intended to be given an antistatic propertyexternally of the surface of the polymer in an aqueous solution without kneading this substance into the polymer. By the use of an effective dispersing agent, the author solubilized and partially dispersed a water-insoluble substance in an aqueous solution to prepare a transparent aqueous solution containing this substance in the state of being dispersed and solubilized therein. By destroying the resulting emulsion and then bonding the particles of this substance in this aqueous solution onto the surface of a polymer, the substance was deposited in an adsorbed state on the surface of the polymer externally. As a result, the author succeeded in forming a water-insoluble molecular surface layer of the said substance on the surface of the polymer.

According to the authors researchwhich was reported in Kogyo Kagaku Zasshi, vol. 68, p. 2186, (1965), it was found that the substance having the chemical structure (I) could be modifiedin case the substance was an alkali earth metal salt such as a salt of calcium or barium-into a quite stable substance having the following chemical formula which was an acid salt of a metal salt of amphoteric surface active agent:

It is, therefore, a primary object of the present invention to provide a new detergent composition not only having satisfactory detergency, bubble formability and bubble durability which are essential requirements of a detergent, but also having the capability of imparting to laundry which is cleansed with it an antistatic property, resistivity to re-soiling and soil releasability.

Another object of the present invention is to provide a new detergent composition of the type described, which not only can be used independently as a detergent, but also which, when included in a small amount in any known detergent, fully exhibits the aforesaid desirable effects.

Still another object of the present invention is to provide a new detergent composition of the type described, which gives laundry which is cleansed with it a long-staying antistatic property, resistivity to re-soiling and soil releasability and which, thus can display the same useful effects for practical purposes as those exhibited by laundry which is given an additional antistatic and other treatments after being washed.

These as well as other objects, advantages and features of the present invention will become apparent by reading the following detailed description of the preferred embodiments.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention contemplates the provision of a new detergent composition which is prepared by the use of at least one of those water-insoluble metal salts of amphoteric surface active agent which are expressed by the general formulas:

/NOH2 /N- Hz My H0 lwnn'onn'm x 2)mCO0 x (III) %NOH;4 %NCH2 RC\ RC\ /NOH2 My CH2 HO CHRCHRObX HO LCER'OHROEX (OHZ)mCOO x Ethic/OOH z 5 OH/Xi l (RH/A {R /CH-CH$ 1 lI---(CH2). N\

k b (CHRCHRO),XJ I (CHR'CHRW X O(CHRCHRO) X l (CH2)mCO0 and if 1 a {R- CHCHz) N(CHZ)B N k l (g l HR'CHRO),X (OHRGHROMX ownn'onn'm x 1 (CHz)mCOO R I if {R-(OH-Cfih} N (CH2)B N dnn'onn'otx OER 011E051:

O(CHRCHRO) X (CH2)COOH wherein:

R represents a hydrocarbon group having 630 carbon atoms;

R represents hydrogen or CH m represents an integer 1-3;

p represents an integer 1 or 2;

X represents hydrogen or (CH COO or (CH COO X may be X or nothing; in the latter case there is present no OH group bonded to nitrogen;

b represents an integer 1 or 2;

k represents an integer 0 or 1;

q, r each represents an integer 0 or 1 or 2;

lrepresents an integer 0 or 1-5;

s represents an integer 14;

M represents an alkali earth metal;

x, y, z each represents an integer determined by the valency of the said metal; and

A represents either -(CHR"CHR'O) X or R-CHCH2 (CHRCHRO)DX and blending the aforesaid water-insoluble metal salt to amphoteric surface active agent having, in the molecules thereof, the following common group:

/ ECHQIDC O O m represents an integer 1-3;

R represents hydrogen or CH X represents hydrogen or (CH COO; and p represents an integer 1 or 2 and blending the aforesaid water-insoluble metal salt to at least one of the substances expressed by the general formula:

wherein (V s represents an integer 1-4;

0 M represents an alkali metal or a non-alkali metal;

x, y, 2 each represents an integer determined by the valency of the metal; A represents either (CHR'CHRO) X or X X X X X X X7 each represents hydrogen or (CH COO (wherein: m represents an integer 1-3; at least one of X X X X X X X is (CH COO; in case X and X are not (CH COO, nitrogen, will be tertiary nitrogen),

and by solubilizing and dispersing the resulting mixture in water in partially solubilized condition. This composition may be used widely as a detergent either independently or by being added in any known detergent, in each of which instances the composition will exhibit an excellent detergency, bubble formability and bubble durability for laundry which is washed with this composition, and moreover, it can give the laundry an antistatic property, a resistivity to re-soiling and a soil releasability of a prolonged duration.

In other words, the detergent composition of the present invention may be regarded as a sort of polymeric electrolyte or polymeric surface active agent, and can be considered to present a dispersion system of high molecular weight micelles, in a solution, of at least one of the aforesaid substances expressed by the general Formulas III, IV, V and VI. Accordingly, the critical micelle concentremely stable bubbles are formed, and moreover, it is possible to have the soil components adsorb or deposit onto the surfaces of the bubbles effectively, and also, after the bubbles have been removed by a vacuum suction device, the carpet surfaces will have excellent antistatic tration of these substances for micelle formation is very property and soil-releasability. low, which appears to be in the order of M -V of the As the metal in (III)-(VI) in the present invention, critical micelle concentration of sodium alkylbenzene sulmetals other than alkali metals which form water-insolufonate. Thus, the detergent composition of the present ble metal salts having a high melting point are selected invention exhibits surface activity at a very low conceuas a principle. More desirably, the use of an alkali earth tration thereof and displays a satisfactory detergency. metal such as calcium and barium is suitable. By the use Furthermore, solubilization and destruction of dispersion of an alkali earth metal, it should be understood that take place at the laundry/washing solution and air/wash- (III) and (V) can form acid salts in the form of (IV) ing solution interfaces, and as a result, a water-insoluble and (VI), respectively. and firm mono-molecular layer is formed by adsorption Hereunder are shown typical substances in order to exof the said composition onto the surface of the laundry. plain the general Formula V in further detail.

0? (OHz)mCOO OH (CH2)mCOO R-CH CH2l :N-(CH2)- N-(CHRCHRO) X My OER tiHCHRCHROMX (iHRcHRmrx OER 0)): x (v-1 0H 011M000 R-CH CH2 N-(CHR'CHR'O),,X] My (CHRCHROMX (OHRCHROMX x (V-2) OH (oHnmooo 0H (cHnmooo R--OH OHz N-(CHz). --N(CHR'CHRO),,X M

i L I CHr-CH R (CHRCHR'm X ((LHRCHRO),X

0(CHRCHRO),X x (V-3 OH (cHomcoo R-CH CH: N-(CHRCHROMX My dwna'onn'onx orn-cn-n (CHRCHROhX x (V4) Accordingly, bubbles which are firm and yet durable are formed very easily. Along with this, a tough mono-molec- OH ular layer of the substance of either (III), (IV), (V) or 40 (CHWCHWWDX (VI) is formed in the same way at the surface of the laundry. Thus, the laundry is imparted an antistatic prop- My erty and at the same time the laundry is effectively pre- )CHRCHWOBX vented from re-deposition thereon of the soil components, especially of oily soil, having been detached previously (CHZMCOO x (7-5) therefrom, thus developing a high re-soiling preventability or soil releasability. OH (011M000 (gaclmmcoo In view of the fact that this mono-molecular surface R-N(CH2). N(CHRCHRO)DX My layer of the substance of (H1), (IV), (V) or (VI) is in- I X CHRICHIVO X v x -15 soluble in water and 1s firm, 1t is held stably at the sur- )q )n face of the laundry in the rinse process also. Moreover, OH (CH) CO 0 the said layer is stably held thereat continuously after the 2 laundry is dried. Thus, the layer of the said substance is )sX M able to impart the laundry'an antistatic property as well y as a soil releasability for an extended period of time. As such, the detergent composition of the present invention (CHR CHR ohx x (V4) can be used independently as a finishing agent for the purposes of antistatic treatment, anti-resoiling treatment, OH (CHDECOO (FECHMCOO soil-release treatment and/or softening treatment. Such h M properties of the composition of the present invention can HRICHRIWX y be as equally exhibited in case it is added to known detergent compositions as is exhibited in case it is used alone. (GER CHR x (v.8) As an example of especially effective instances, this com- Accordingly, in order to explain the general Formula position is added to a known carpet shampoo consisting VI in further detail, its typical substances are shown as mainly of sodium salt of alkyl sulfate. By doing so, exfollows:

(C Z)mCOO (CHZ)mCOO OH OH CHnmCoo CH2)mCOO R-CH-CH N-(0H),- N-(CHRCHRO)DX My- R-CHCH2 {N(CH2)s' (CHRCHR'O ,X X CHRCHR'O),X (CHR'CHRO),X HRCHRO),X HR'CHROLX (CHRCHR'O) X (CHROHROMX z (VI-1) The metallic group which can be used in (VII) may 5 consist of the same metallic group as those stated above OH X2 (CHRCHRO),X so as to correspond to those in (III), (IV), (V) and (VI), respectively. However, it is also possible to utilize R-CH-CHz--N those metallic groups of alkali metals and non-alkali metals of a broad range. 5 E

In order to explain the general formula of (VII), its (CHR/CHR/mpm \OwHRCHRIWDm x (VIM) typical substances may be enumerated as follows:

HRCHRO X CHRCHRO X )q 4 a x (VII-5) (CHRCHROhXa 2;

OH X1 OH i I (VII-1) 0H X1 OH X2 CHRICHRIWJQ Solubilization and dispersion in water may be ac- I I complished by first heating at least one of the substances N (III) through (VI) to a temperature of -120 C. (in MY case the substance is of a high melting point, it is heated HRCHRO) X4 CH2-CHR at a temperature above C. but about 5 C. lower than (CHKCHIVOMX O(CHR,CHR,O)DX7 X its melting point) in either anhydrous state or hydrous (VH 3) 75 state, thereafter adding thereto a substance of (VII) heated to the same temperature while stirring the mixture thoroughly and cooling same down to 80-90 C., and adding a predetermined amount of water of the same temperature, followed by a thorough stirring and cooling the resultant mixture to room temperature. Desirably, this mixture is further passed through a colloid mill or a homogenizer in order to obtain a much better and more stable aqueous dispersibility.

An even more desirable composition of the present invention may be obtained by adding to the aforesaid composition a metal salt (such as a salt of lithium, potassium or calcium) of acylated amino acid or other surface active substances.

EXAMPLE 1 HzCHzOH 2 parts by weight of a compound having the above mentioned structural formula were heated at 100 C. and melted. While stirring, 2.2 parts of a substance selected from those having the structural formulas (A) through (F) mentioned below and held at the same temperature were added thereto to melt the added substance uniformly. Then, 87.8 parts of boiling water which was prepared separately were added little by little while stirring to dilute the mixture. After the completion of the addition, the resulting mixture was passed once through a homogenizer and was cooled to normal temperature. As a result, a paste-like composition was obtained.

CHzCH)15H OH CHzCOO OH CHICOO Cra 31--N(CHz)a (CH2CH20)20H Ca HzCHzO)2o (CHzCHzO)tnE (F) Pieces of knitted fabric made of acrylic fibers (a product of Mitsubishi Rayon Co., Ltd. of Japan, marketed under the trade name of Vonnel) were allowed to sustain deposition thereon of an oily soil consisting of liquid paraffinzsoya bean oil=1:1. Thereafter, these soiled pieces of knitted fabric were washed by an electric washing machine. The result is shown in Table 1.

TABLE 1 Antistatle property Detergeucy Half of oily time of Softsoil leakage Surface ness (per- (seeresistlv- (hand Detergent cent) 0nd) ity (Q) feel) 97 0. 1 1. 1X10 Suit. 98 0. 1 2. 3X10 DO. 98 0. 1 4.1X10' Do. 97 0. 1 3. 3X 10 Do. F 96 0. 1 5. 1X10 D0. Commercial heavy duty detergent 97 0. 1 1.1X10 Do.

(N0. 2) 72 00 10" Rigid.

N0'rE.The composition of the Commercial heavy duty Detergent No. 2 is: sodium salt of linear alkylbenzeue sulfonate 26%, sodium salt of tripoly phosphoric acid 24%, sodium disilicate 5%, soda ash 5%, and Glaubers salt 40%.

EXAMPLE 2 CHnOOOH 2 CHzCHzOH HO l 011,000 2 10 parts by weight of a compound having the abovementioned structural formula were blended with 2 parts of a compound selected from (A) through (F) used in Example 1 in the same manner as that described in Example 1. The resulting mixture was diluted with 88 parts of water and a paste-like composition was prepared. In the same way as that in Example 1, a washing test was conducted, The result is shown in Table 2.

wherein R represents a saturated hydrocarbon group having 18-26 carbon atoms.

To 8 parts by weight of a substance having the abovementioned structural formula were blended 2 parts of a compound selected from (A) through (F) in the method similar to that described in Example 1. The resulting mixture was diluted with 90 parts of water and a liquidous composition was prepared. In the same way as that 1 1 in Example 1, Washing test was conducted. The result is shown in Table 3.

TABLE 3 Antistatic property Detergency Half of oily time of Softsoil leakage Surface ness Type of (VII) (per- (secresistiv- (hand used in the detergent cent) ond) ity (fl) feel) 92 O. 1 2. 8X10 Soft. 93 0.1 1 1X10 Do. 96 0.1 3 2X10 Do. 91 0.1 5 3X10 D0. 96 0.1 7 7X10 D0. F 94 0.1 6. 8X10 Do. Commercial heavy duty 72 10 Rigid.

detergent.

EXAMPLE 4 CH2CH2OH RCHCHz-N Ca H CHzCHzOH CHZCOO 2 wherein R represents a saturated hydrocarbon group having 1826carbon atoms.

To 8 parts by weight of a compound having the abovementioned structural formula were added 2 parts of com pound selected from (A) through (F) in the same manner as that described in Example 1, followed by dilution with 90 parts of water, and a liquidous composition was prepared. In the same way as that in Example 1, a washing test was conducted. The result is shown in Table 4.

TABLE 4 Antistatie property Detergency Half of oily time of Softsoil leakage Surface ness Type of (VII) (per- (seeresistiv- (hand used in the detergent cent) ond) ity (S2) feel) 96 0.1 1 9X10 Soft. 97 O. 1 3 6X10 Do. 98 0.1 1 0X10 D0. 95 0.1 4 6X10" Do. 94 O. 1 3 2X10 Do. F 96 0.1 e 1x10 p Commercial heavy duty 72 w 10 Rigid detergent.

EXAMPLE 5 OH OHzCOO wherein R represents a saturated hydrocarbon group having 1416 carbon atoms.

To 7 parts by Weight of a substance having the abovementioned structural formula were blended 3 parts of a compound selected from (A)-(F) in Example 1 in the same manner as described therein, followed by dilution with 90 parts of water, and a liquidous composition was prepared. A washing test was conducted in the same manner as that in Example 1. The result is shown in Table 5.

TABLE 5 Antistatic property Detergency Half of oily time of Soft soil leakage Surface ness Type of (VII) (per- (secresistiv- (hand used in the detergent cent) ond) ity (f2) feel) A 91 0. 1 3.6X 10 Soft. B 90 0.1 9.2)(10 Do. C 93 0.1 1 0X10" Do. D 92 0.1 6.8) 10 Do. E 95 0. 1 3 3X10 D0. F 90 0. 1 2 9x10 D0. Commercial heavy duty 72 oo 10 Rigid.

detergent.

wherein R represents a saturated hydrocarbon having 18-26 carbon atoms.

To 7 parts by weight of a compound having the abovementioned structural formula were blended 3 parts of a compound selected from (A) through (F) in the same manner as that in Example 1. By diluting the mixture with parts of water, the desired composition was prepared. In the same manner as that in Example 1, washing test was conducted, the result of which is shown in Table 6.

TABLE 6 Antistatic property Half time of leakage (second) Detergency of Soft- Surface ness resistiv- (hand ity(Q) feel) 9.6X 10" Soft. 8.1 X 10 D o. 5.0)(10 DO. a7 10 Do. 4.6X10 D0. 6.6X10 D0.

10 Rigid.

Type of (VII) used in the detergent Commercial heavy duty detergent.

EXAMPLE 7 (3113 OH CH2CHOH C raHav Ca CHzCHOH CHzCOO CH3 2 To 8 parts by weight of a compound having the abovementioned structural formula were blended 2 parts of a compound selected from (A) through (F) in the same manner as that in Example 1, followed by diluting with 90 parts of water, and as a result, the desired composition was prepared. Washing test was conducted in the same manner as that in Example 1. The result of the test is shown in Table 7.

To 9 parts by weight of a compound having the abovementioned structural formula was blcnded 1 part of a compound selected from (A) through (F) in the same manner as that in Example 1, followed by dilution with 90 parts of water, and thus the desired composition was prepared. The result of washing test conducted in the same manner as that in Example 1 is shown in the followwherein R represents a saturated hydrocarbon having mg Table 8. 14-16 carbon atoms.

TABLE 8 To 9 parts by weight of a compound having the above- A fist f T It mentioned structural formula was added 1 part of a com- Detep w pound selected from (A) through (F) in the same mangenpy Half ner as that in Example 1, followed by dilution with 90 of oily time of Soft- Soil leakage surface ness parts of Water, and thus the desired composition was pre- Type of(VII) (p resistiv- (hand pared. Washing test was conducted in the same manner l o 1 usedm the detergent cent) mi) fee) as that in Example 1. The result of this test is as shown 90 0:1 1.0x Soft. 89 0.1 32x10 Do. 10 m Table 90 0.1 4.4)(10 Do. T ABLE 10 91 0. i 1.235 1 go. 90 0. 1.0 0. 92 0.1 asxm D o. Deterw Commercial heavy duty deter- 72 1 Rlgldgeney Half gent. of oily time of Soft- T {MD (soil lealirage Surftaee 3555a ype 0 persec- T8518 7- an EXAMPLE 9 used in the detergent cent) 0nd) ity (n) feel) 2% 3-: 2-2223: 0 COO 0. 22 a: are: a- C CH 0 H o. CraHar H: s )2 Ca F 3 1 g 0 R 0. cm H Commercial heavy duty deter- 72 00 10 Rig O CH2CH20)2H 2 gent.

EXAMPLE 11 OH 0112000 on CHzCHzOH OH OHZCOOH OH CHZCHZOH Ba. R-CHCHz-N(CH2)2N AHZCHZOH l mcnzon l memoir l ornomon OCH2CH2OH H2000 CHzCHzOH HaCOOH wherein R represents a saturated hydrocarbon having 1826 carbon atoms. wherein R represents a saturated hydrocarbon havlng To 9 parts by Weight of a compound having the above 18-26 carbon atomsmentioned structural formula was added 1 part of a com- 8 Parts by might of a compound havmg the above pound selected from (A) through (F) in the same manmentioned structural formula were blended 2 parts of as that in Example I, followed by dilution with 90 a compound sekjcted from (A) through (F) t m parts of water, and thus the desired composition was manner as that Example followed by d1 1ut1n Wlth prepared. A washing test was conducted in the same man- 90 parts of water in the same manner as that in Example Her as that in Example L AS a result, superior hand and thus the desired CPmPQSitiOH was Prepared' feel, detergency and antistatic property as compared with test was conducted i m as that m those of commercial heavy duty detergents were demon- Example 1. The result of this test 1s shown in Table 9. Stated as in Example EXAMPLE 12 OH CH2CH2OH 0H CHZCHZOH RCH--CHz-N C R-CH-CHz-N 8 bit l CHzCHzOH H l CH2CH2OH H1000 2 HzCOOH 2 TABLE 9 Antistatic property Detergeney Half 3 35 233;; surface wherein R represents a saturated hydrocarbon having Type f (VII) (per- (secresistiv- (hand 18-16 CfllbOD atoms. used in the detergent cent) mm) 1W (a) feel) To 8 parts by weight of a compound having the above- 92 0.1 3.6X10 Soft. mentioned structural formula were blended 2 parts of a g? 8:} 2:383: g8: compound selected from (A) through (F) used in Ex- 93 0.1 rsxm Do. ample 1, followed by being diluted with 90 parts of F 3% 8 iggggifi 33: water, and thus the desired liquidous composition was Commercial heavy duty deter 72 co 10 Rigid. prepared. A washing test was conducted in the same e manner as that in Example 1. The result was that superior hand feel, detergency and antistatic property were demon- EXAMPLE 10 strated as in the case of Example 4. OH 0112000 0H 0111000 01211131 (CHz)a--NCHrCHzOH Ca HQCHZOH H2 0 H-R OCHQCHZOH EXAMPLE 13 OH /CHC0O 0H CHZCOO 0H CHzCOOH 0H CHZCOOH R-CH--CHz N-CH2CHz- CH2CHOH C RCHCHzN--CHzCHz-N-CH1CH2OH a. 001120112011 CHZCHZOH CHz-CH-R CHzCHrOH CHzCH-R I OHzCHzOH OCHzCHzOH 16 wherein R represents a saturated hydrocarbon having 18-26 carbon atoms. EXAMPLE 17 OH CHzCOO OH OH2COOH C1sH 7N(CH2CHz0)2H C C1sH 7N(CHsCH20)2H Hz-CH-R HzCH-R (CH2CH20)2H 2 O(CHzCHzO)2H 2 To 8 parts by weight of a compound having the above- To 8 parts by weight of a compound having the abovementioned structural formula was blended 1 part of a mentioned structural formula were blended 2 parts of a compound selected from (A) through (F) in the same compound selected from (A) through (F) in the same manner as that in Example 1, followed by dilution with manner as that in Example 1, followed by dilution with 90 parts of water, and thus the desired liquidous com- 90 parts of water. Thus, the desired composition was preposition was prepared. In the same manner as that in pared. This composition was then subjected to a washing Example 1, a washing test was conducted. The result was test. As a result, superior effects as those in Example 9 that superior hand feel, detergency and antistatic propwere noted. erty same as those in Example 5 were noted. EXAMPLE 18 CHzCOO CHzCOOH OH OH CHzCOO OH OH OHzCOOH C1gH37 N(CH2)3NCH2CH2OH Ca- C1BH37N-(CH2)3N-OH2OH2OH HzCHR Hz-CHR CHzCHzOH OCHzCI-IzOI-I CHzCHzOH OCHzCHzOI-I EXAMPLE 14 OH COzCOO OH CHaCOOH R-(EH-OH: NCHzOH2OH RCHCH2 N-CHzCHzOH a. O H CH2(: H-R H CH2 C H-R OH H 2 wherein R represents a saturated hydrocarbon having wherein R represents a saturated hydrocarbon having 14- 18-26 carbon atoms. 16 carbon atoms.

To 7 parts by weight of a compound having the above- To 9 parts by weight of a compound having the abovementioned structural formula were blended 3 parts of a mentioned structural formula was added 1 part of a comcompound selected from (A) through (F) of Example pound selected from (A) through (F) in the same man- 1, followed by being diluted with 90 parts of water to nor as that in Example 1, followed by dilution with 90 prepare the desired composition. In the same manner as parts of water to prepare the desired composition. A washthat in Example 1, a washing test was conducted. The ing test was conducted by the use of this composition. The result sho ed superior efi t as i E am l 6, result showed as satisfactory effects as those demonstrated in Example 10. EXAMPLE 15 EXAMPLE 19 OH OH CH 3 3 Commercial detergent used 1n th s example had the CHNHOH OHZCHOH following composition: 12% of sodium salt of linear alomH N Ca. 018mm kylbenzene sulfonate, 15% of sodium tripoly-phosphate and an amount of Glaubers salt which was increased to OH CHOH CH CHOH 2 2 63%. To a batch of this commerclal detergent composi- CHZCOO CH3 2 GHZCOOH CH3 2 tion was added 10% of a composition selected from those To 8 parts by weight of a compound having the aboveobtained in the above-mentioned examples, i.e., the commentioned structural formula were blended 2 parts of a position containing (B) and the composition containing compound selected from (A) through (F) in the same (E) in Example 1; the composition containing (B) and manner as that in Example 1, followed by dilution with 90 the composition containing (E) in Example 2; the comparts of water to prepare the desired composition. A washposition containing (B) and the composition containing ing test was conducted with this composition. The result (E) in Example 4; and the composition containing (B) was that superior eifects as those in Example 7 were ex and the composition containing (E) in Example 12. They hibited. were added, respectively, one for one batch, Thus, deter- EXAMPLE 16 gent compositions were prepared. By the use of these re- CH3 CH3 CH3 CH3 OH CHMJJHOH OH CHzfIHOH OH (FHzlHOH OH CHZOHOH C18H37N(CHz)3-N Ba- C1\I(OH2)3N H2000 CHZCHOH HzCOOH CHZCHOH CHZCOO lHa CHzCOOH 6H3 To 9 parts by weight of a compound having the above- Spective detergent compositions, washing tests were conmentioned structural formula was added 1 part of a comducted on pieces of soiled polyester cloth (these pieces of pound selected from (A) through (F) in the same manclothproduct of Teijin Co., Ltd. of Japanwere atner as that of Example 1, followed by dilution with tached to the inner side of the collar of shirts and worn parts of water. Thus, desired composition was prepared. by persons consecutively for a week to become soiled) in This was subjected to a washing test, with the result that the same manner as that described in Example 1. The resuperior effects as those in Example 8 were noted. 7 sult of these tests is shown in Table 11.

TABLE 11 Hair was washed with these compositions, respectively.

antistatic property The result is shown in Table 13. TABLE 13 Percent- Half Softage of time of Surface ness Static soil leakage resistiv- (hand frictional Detergent removed (second) ity (S2) feel) Sh coefli; f l

BIHDOO cten 88 (B), Example 1 98 0.1 2.0X' Soft. (E), Example 1... 98 0.2 4.5X101 D0. (B), Example 1 0.201 (B), Example 2..- 97 0.2 7.3Xl0 Do. (E), xample 1.- 0.198 do (E), Example 2 96 0.3 1. 0X10 D0. (B), Example 2-. 0.190 -do (B), Example 4 98 0. 1 8. 6Xl0 Do. 10 (E), Example 2 0. 197 do (E Example 4. 97 0. 1 5.0X10 Do. (B) Example 4" 0. 197 0 (B Example 12 97 0.4 8.0X101 Do. (E), Example 4 0. 196 do (E), Example 12 98 0.5 1. 0X1011 Do. (B), Example 12... 0. 200 Commercial heavy duty deter- 76 10" Rigid (E), Example 12 0. 199 -..do...

gent. Commercial shampoo (control) 0. 230

15 EXAMPLE 22 Those compositions shown in the foregoing examples EXAMPLE were further diluted to M with water. Pieces of a knitted Carpet cleaning solution having the following two types fabr 10 made of i fibers. (product Toray of compositions were prepared 20 of Japan) were lmmersed 1n the solut1on at the bath who of 1:30, at 30 C. for 5 minutes. Then, the pieces of fabric were squeezed to about 50%. After being air- Detergent composition of the present invention: Percent dned at room temperature they Wei-.6 felt to deiermme Composition of th invention 0 1 the softness. Thereafter, the treated pieces of fabrlc were Sodium Salt of lauryl Sulfate 0.425 25 Washed a cornmerclal vy y detergent under Laumyl diethanolamine 0 15 the washing cond1t1ons stated 1n example. Thereafter, Wat?r Balar'lce they were soaked for 12 hours in a sufficiently soiled solu- Control ga g g; tion prepared by Washing soiled underwears with a com- Sodium Salt of lauryl Sulfate 0 5 mercial heavy duty detergent until bubbles ceased to Lauroyl diethanolamine 0 5 form. After being air-dried at room temperature they Water Balat'lce were determined of the soil additional density (SAD) (log R /R wherein: R represents reflectance before being soiled, and R represents reflectance after being Y use these two yp of detergent P soiled). The result 1s shown 1n Table 14. From this table, solled llght PTOWH fp made of fy fibers it is known that the compositions of the present invention w washed accordugg to r p y carpet washlng ngethofl, impart soft feel and antistatic property to laundry. 1.e., bubble formation-brushmg-leavmg them lylng 1n TABLE 14 bubbles-vacuum suction. The result of the washing test is as Shown i Table 12 After treatment After treatment-washing 40 Half Half time of time of leakage leakage Hand (sec- Hand (sec- SAD TABLE 12 Composition feel onds) feel onds) (X104) (B), Example 1 Soft. 01 Soft..... 0.1 432 itaitatmy a, g Example g 3-1 g3; Degree upon completime of E2331: 1 g 1 427 0f Soil 9 akage Reason (B); Example 4: 011 IIIduIIIII 01 1 39s Detergent removed waslung (seconds) (days) g k i g xam e 0 Example g g f g d 67 (E), nxamgle 12 ..do... 0.1 do 0.1 379 1 Commercial household Fair" 7.0 Rigid--- 28.0 820 (E),Example1 do ..do 1.0 55 Sumner (B), Example 2-- do do 0. 6 70 E i: i ----gg--- 8-}, What is claimed is: 323 "1 1: 60 l. A detergent composition, consisting essentially of -g 3 one of the water-insoluble metal salts of amphoteric sur- Coritrol--.. till mid :1 (x. 13 face active agent which are expressed by the general forsome 501 W en u touched. mulas' 1 Carpets were laid at the entrance of a building. The number of days iNCH2 required for being soiled to almost the same degree as noted before being R C washed was calculated from floor test. The carpets were, however, cleaned once every day by an electric cleaner. N M

H0 LCHRCHR'OBX Ht)m (III) EXAMPLE 21 N CH, N c Ha1r shampoo composltlons were prepared by adding C I R-C 10% of the compositions of the present invention (containing 90% of water) to batches of the following hair k Shampoo composition: HO (CHRCHRm X My H0 HRCHR'0),,X

(cflnmcoo x 2)mCOOH Parts (IV) Triethanol amine lauryl sulfate 8 wherein Lauroyl diethanolamine 3 Urea 8 R represents an alkyl group having 6-30 carbon atoms; Sodium salt of tri-lauryl alcohol ether surface 3 R represents hydrogen or CH Water Balance m represents an integer of 1 to 3;

p represents an integer of 1 to 2; X represents hydrogen, (CH COO or (CH COOH M represents an alkaline earth metal; x, y and z each represent an integer determined by the valency of said metal;

said water-insoluble metal salt being blended with at least one substance expressed by the general formula:

X and X represent hydrogen, (CH COO or nothing:

X X X X and X; each represent hydrogen or t is 1 when X or X is hydrogen or (CH COO and t is 0 when X or X is nothing.

2. An aqueous composition consisting essentially of the detergent composition of claim 1 being at least par-- tially solubilized or dispersed in water.

3. A detergent composition according to claim 1, in which the said water-insoluble metal salt is one expressed by the general Formula III. 7

4. A detergent composition according to claim 1, in which the said water-insoluble metal salt is one expressed by the general Formula IV.

5. A detergent composition consisting essentially of the detergent composition of claim 1 blended with an organic sulfate or organic sulfonate detergent.

6. A detergent composition consisting essentially of the detergent composition of claim 3 blended with an organic sulfate or organic sulfonate detergent.

7. A detergent composition consisting essentially of the detergent composition of claim 4 blended with an organic sulfate or organic sulfonate detergent.

References Cited UNITED STATES PATENTS 3,660,142 5/ 1972 Kasugai 260-l.13

FOREIGN PATENTS 3,813,388 6/1963 Japan.

MAYER WEINBLATI, Primary Examiner E. ROLLINS, Assistant Examiner US. Cl. X.R. 

